Surfactant-induced aggregation patterns of thiazole orange: a photophysical study

The aggregation behavior of the DNA marker dye thiazole orange (TO), has been investigated in two types of surfactant assemblies, namely, premicelles/micelles of sodium dodecyl sulfate (SDS) and pre reverse micelles/reverse micelles of sodium bis(2-ethylhexyl) sulfosuccinate (AOT). In the case of an SDS/water system, absorption spectral changes of TO signify the formation of H-aggregates and H-dimers of the dye at premicellar concentrations, which subsequently convert to the monomeric form beyond the critical micellar concentration (cmc). Interestingly, the observed changes in the absorption and emission characteristics due to the surfactant-induced formation of H-aggregates/dimers of TO are found to be useful to estimate the surfactant concentration parameters for premicellar aggregation of SDS. In the case of an AOT/n-heptane system, similarly, H-aggregates/dimers are observed at low AOT concentrations, below the cmc. However, in this case, the H-dimers persist even beyond the cmc. This is attributed to the strong tendency of TO for self-aggregation and its favorable electrostatic interactions with the AOT head groups. With increasing water content in the AOT reverse micelles, the hydration of the dye leads to the conversion of H-dimers to the monomeric form. The steady-state fluorescence results are nicely corroborated with those from time-resolved fluorescence studies and demonstrate the interesting behavior of the surfactant-induced aggregation of TO dye.     

Analysis of interfacial and micellar behavior of sodium dioctyl sulphosuccinate salt (AOT) with zwitterionic surfactants in aqueous media

The interfacial and bulk properties of mixtures of the anionic surfactant (dioctyl sulphosuccinate sodium salt, AOT) with zwitterionic surfactants 3-(N,N-dimethyldodecylammonio) propane sulfonate (DPS), 3-(N,N-dimethyltetradecylammonio) propane sulfonate (TPS), 3-(N,N-dimethylhexadecylammonio) propane sulfonate (HPS) have been studied employing surface tension, fluorescence, and viscometric techniques in aqueous media at 25 °C. It is observed that these mixtures exhibit synergism and these synergistic interactions increase with the enhancement of the hydrocarbon chain of the zwitterionic surfactant. The various physicochemical properties such as critical micelle concentration (cmc), surface excess concentration (Г(max)), minimum area per molecule (A(min)), aggregation number (N(agg)), interaction parameters (β(σ), β(m)), and thermodynamic parameters such as standard Gibbs free energy of adsorption (ΔG(ads)(o)), excess free energy of micellization (ΔG(ex)), and standard Gibbs free energy of micellization (ΔG(m)(o)) have been evaluated. The negative values of ΔG(m)(o) and ΔG(ads)(o) show that the micelle formation and adsorption of surfactant at the air/solution interface is energetically favorable, while a negative value of ΔG(ex) ensures stability of the mixed micelles formed. The Regular Solution Approximation, Motomura and Rosen's approaches have been used to explain and compare the results. The packing parameter (p) ensures the formation of vesicles or bilayers for AOT+DPS/TPS mixtures, which can potentially be used as delivery agents for industrial applications.     

Molecular dynamics study of micellization thermodynamics in AOT/hexane system

The thermodynamics of reverse micelle formation from an ionic surfactant, sodium bis(2-ethylhexyl) sulfosuccinate (Aerosol OT, AOT), in hexane is studied by molecular dynamics simulation. A change in the Gibbs free energy upon the addition of one AOT molecule to a reverse micelle is calculated as depending on aggregation number N by the thermodynamic integration method. This dependence has a minimum at N ≈ 20 and maximum at N ≈ 35 and predetermines the monotonically decreasing character of the standard chemical potential of AOT in a micelle with the increase of the aggregation number. The simulation results predict the formation of reverse AOT micelles with an average aggregation number of ≈30, which is in good agreement with experimental data.     

Effect of compressed CO2 on the properties of lecithin reverse micelles

Lecithin is a very useful biosurfactant. In this work, the effects of compressed CO 2 on the critical micelle concentration (cmc) of lecithin in cyclohexane and solubilization of water, lysozyme, and PdCl 2 in the lecithin reverse micelles were studied. The micropolarity and pH value of the polar cores of the reverse micelles with and without CO 2 were also investigated. It was found that CO 2 could reduce the cmc of the micellar solution and enhance the capacity of the reverse micelles to solubilize water, the biomolecule, and the inorganic salt significantly. Moreover, the water pools could not be formed in the reverse micelles in the absence of CO 2 because of the limited amount of water solubilized. However, the water pools could be formed in the presence of CO 2 because large amounts of water could be solubilized. All of these provide more opportunity for effective utilization of this green surfactant. The possible mechanism for tuning the properties of the reverse micelles by CO 2 is discussed.     

离子液体1-烷基-3-甲基咪唑四氟硼酸盐在水溶液中的聚集行为

采用等温滴定量热法、静态荧光猝灭法和电导法系统研究了典型离子液体1-烷基-3-甲基咪唑四氟硼酸盐([Cnmim][BF₄])在水溶液中的聚集行为, 获得了胶束形成的临界胶束浓度(cmc), 摩尔焓变(ΔH_mic), 摩尔吉布斯自由能变(ΔG_mic), 摩尔熵变(ΔS_mic)以及不同浓度时[Cnmim][BF₄]胶束的平均聚集数等基本参数. 发现这类离子液体的聚集为熵驱动, 阳离子的烷基链越长, ΔG_mic越负, 聚集更容易发生. 此外, 结合[C_nmim]X (X=Cl^-, Br^-)的相关研究发现, 阳离子相同时, 体积越大和疏水性越强的阴离子与头基的结合能力越强, 能有效地降低头基之间的静电排斥, 降低cmc, 利于胶束的形成. 对于[C₁₂mim][BF₄], 添加剂β-环糊精(β-CD)的加入可使cmc增大, ΔH_mic和ΔS_mic减小, 而KBF₄则可使cmc和ΔH_mic减小, ΔS_mic增大.     

Specifics of the formation of J-aggregates of cyanine dyes in solutions of AOT/water/hexane reverse micelles

The behavior of a cyanine dye (3,3′-di-(gamma-sulfopropyl)-4,5,4′,5′-dibenzo-9-ethylthiacarbocyanine betaine pyridinium salt) was studied in AOT/water/hexane reverse micelles over a wide range of W at various concentrations of the dye, AOT, and reverse micelles. The processes occurring during the formation of the AOT/water/hexane micellar solution were studied in detail. It has been shown that, before the formation of the stable microemulsion, the dye aggregation processes occur by virtue of the interaction of the dye with the AOT anion. The amount of J-aggregates is proportional to the logarithm of the ratio of the amount of AOT molecules to the amount of dye molecules. The time behavior of J-aggregates after the formation of a micellar structure depends on the concentration of reverse micelles, thereby indicating an important role of intermicellar exchange.     

Intermicellar material exchange in reverse micelles formed by ionic AOT and nonionic Igepal surfactants studied by means of pulse radiolysis. Influence of the temperature

The recombination of thiocyanate anion radicals, (SCN) ₂ ⁻ , formed pulse radiolytically within the water pools of reverse micelles stabilized with anionic AOT and nonionic Igepal surfactants, was proved as an indicator reaction to study intermicellar exchange. It was found that the exchange process is slower inIgepal than in AOT reverse micelles with the same water to surfactant ratio. The apparent activation enthalpy and entropy of the exchange process were determined in different alkanes. For the AOT and Igepal reverse micelles the activation parameters increase with the droplet size, but for the AOT systems they do not significantly change with the increase of droplet concentration. For non-percolated systems the activation parameters for Igepal reverse micelles approach those for AOT reverse micelles. This result supports existing suggestions that the mechanism of intermicellar exchange does not differ in principle between reverse micelles stabilized with ionic and nonionic surfactants.     

Comparative studies on the micellization of sodium bis(4-phenylbutyl) sulfosuccinate and sodium bis(2-ethylhexyl) sulfosuccinate and their interaction with hydrophobically modified poly(acrylamide)

The micellization process of sodium bis(4-phenylbutyl) sulfosuccinate (SBPBS) has been studied compared to that of sodium bis(2-ethylhexyl) sulfosuccinate (AOT) by surface tension, steady-state fluorescence, microcalorimetry, dynamic light scattering (DLS), and transmission electron microscopy (TEM) measurements. Meanwhile, the interaction of these two surfactants with hydrophobically modified poly(acrylamide) (HMPAM) was investigated. The results show that the surface tension at the critical micelle concentration (cmc) of SBPBS and the micropolarity probed by pyrene in SBPBS aggregates are both larger than those of AOT. The enthalpy change of micellization (DeltaH(mic)) of AOT is endothermic, while it is exothermic for SBPBS. Strong pi-pi interaction among the adjacent phenyl groups of SBPBS molecules is likely the cause for the above properties of SBPBS. Moreover, vesicles are observed for AOT and SBPBS by DLS and TEM, especially for AOT, whose micelle-vesicle transition has been first confirmed by its calorimetric curve. In the surfactant-HMPAM systems, the critical aggregation concentration (cac), the saturation concentration of aggregation (C(2)), and the thermodynamic parameters of binding have also been determined. The conclusion may be drawn that the binding strength of SBPBS onto HMPAM is stronger than that of AOT.     

Thermodynamics of interaction between sodium bis(2‐ethylhexyl) sulfosuccinae and polymers in aqueous solutions by isothermal titration microcalorimetry

The interactions between sodium bis(2‐ethylhexyl) sulfosuccinae (AOT) and two nonionic water‐soluble polymers, including polyvinyl pyrrolidone (PVP) and polyethylene glycol (PEG) have been investigated by using isothermal titration microcalorimetry in aqueous solutions at 298.15 K. The results show that the critical aggregation concentration, which corresponding to the first turning point in the curve of experimental interaction heat versus concentration of the surfactant, is lower than the critical micellar concentration (cmc), confirming the existence of polymer‐surfactant interactions. The value of cac is not sensitive to the relative amount of polymer in low concentration range of the polymer. The mono‐layer saturated adsorption concentration, which corresponding to the second turning point, rises as the polymer concentration is increased. The interaction between PVP and AOT is stronger than that between PEG and AOT. The results also indicate that the aggregation of AOT in water and polymers solutions is entropically driven. The observed thermal effects have been interpreted in terms of the interactions of the polymer molecules with AOT monomers or the molecular clusters. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 275–283, 2006     

Enhanced solubilization of bovine serum albumin in reverse micelles by compressed CO2

The effect of compressed CO2 on the solubilization of bovine serum albumin (BSA) in water/sodium bis-(2-ethylhexyl) sulfosuccinate (AOT)/isooctane reverse micelles was studied by observing phase behavior and recording UV-visible spectra under different conditions. The pH values within the water cores of reverse micelles at different CO2 pressures were also determined. The solubilization capacity of the reverse micelles for the protein increased considerably as CO2 pressure increased within the low-pressure range, but decreased at higher CO2 pressures, so that the micelles eventually lost their ability to solubilize the protein. The effect of CO2 on the stability of the reverse micelles played an important role in the relationship between pressure and protein solubility. A "multicomplex" model was proposed to explain these effects. The different solublization capacities within different pressure ranges demonstrates the unique advantage of using compressed CO2 in the extraction of proteins with reverse micelles.     

Thermodynamics of demicellization of mixed micelles composed of sodium oleate and bile salts

Isothermal titration calorimetry (ITC) was used to determine the critical micelle concentration (cmc) and the thermodynamic parameters associated with the demicellization of sodium oleate (NaO) and mixed micelles composed of the bile salt (BS) sodium cholate (NaC) or sodium deoxycholate (NaDC), respectively, and NaO at a molar ratio of 5:2. The influence of the ionic strength (pure water and 0.1 M NaCl at pH 7.5) as well as that of the temperature (10-70 degrees C) were analyzed. For NaO, two cmc's were detected, indicating a two-step aggregation process, whereas only one cmc was observed for the two BSs. A single aggregation mechanism is also evident for the demicellization of mixed micelles (BS/NaO 5:2). Increasing the ionic strength induces the well-known decrease of the cmc. The cmc shows a minimum at room temperature. The cmc(mix) of the mixed micelles was analyzed using models assuming an ideal or nonideal mixing behavior of both detergents. The thermodynamic parameters describing the enthalpy (deltaHdemic), entropy (deltaSdemic), and Gibbs energy change (deltaGdemic), as well as the change in heat capacity (deltaCp,demic) for demicellization, were obtained from one ITC experiment. From the temperature dependence of deltaHdemic, the change of the hydrophobic surface area of the detergents from the micellar into the aqueous phase was derived. In all cases, the deltaCp,demic values are positive. In addition, the temperature dependence of the size of the formed aggregates was studied by dynamic light scattering (DLS). DLS indicated two populations of aggregates in the mixed system, small primary micelles (0.5-2 nm), and larger aggregates with a hydrodynamic radius in the range of 50-150 nm.     

Oxidative refolding of reduced, denatured lysozyme in AOT reverse micelles

The refolding kinetics of the reduced, denatured hen egg white lysozyme in sodium bis(2-ethylhexyl)sulfosuccinate (AOT)-isooctane-water reverse micelles at different water-to-surfactant molar ratios has been investigated by fluorescence spectroscopy and UV spectroscopy. The oxidative refolding of the confined lysozyme is biphasic in AOT reverse micelles. When the water-to-surfactant molar ratio (omega 0) is 12.6, the relative activity of encapsulated lysozyme after refolding for 24 h in AOT reverse micelles increases 46% compared with that in bulk water. Furthermore, aggregation of lysozyme at a higher concentration (0.2 mM) in AOT reverse micelles at omega 0 of 6.3 or 12.6 is not observed; in contrast, the oxidative refolding of lysozyme in bulk water must be at a lower protein concentration (5 microM) in order to avoid a serious aggregation of the protein. For comparison, we have also investigated the effect of AOT on lysozyme activity and found that the residual activity of lysozyme decreases with increasing the concentration of AOT from 1 to 5 mM. When AOT concentration is larger than 2 mM, lysozyme is almost completely inactivated by AOT and most of lysozyme activity is lost. Together, our data demonstrate that AOT reverse micelles with suitable water-to-surfactant molar ratios are favorable to the oxidative refolding of reduced, denatured lysozyme at a higher concentration, compared with bulk water.     

脂肪酸十二烷基铵在四氯化碳中的聚集行为

通过碘光谱法和对水的增溶研究了乙酸十二烷基铵(DAA)、丙酸十二烷基铵(DAP)和丁酸十二烷基铵(DAB)在四氯化碳中的聚集作用; 碘光谱测得的(cmc)~I约比水增溶法测得的(cmc)~W低一个数量级。可能因为碘光谱法测得的是开始发生聚集时的cmc, 这时聚集体较小, 对水无增溶能力; 只有当聚集体随浓度升高而长大到一定程度时, 才能开始增溶水。实验表明, DAA, DAP和DAB的反胶束对水的饱和增溶能力, 分别相当于每一个表面活性分子增溶4.2, 9.4和13.5个水分子。根据球型反胶束模型, 计算了反胶束聚集数、捕集水团的半径和自由水团的半径。     

高压CO~2对反胶束溶解蛋白质性质的影响

在308.15K下,研究了表面活性剂琥珀酸二(2-乙基己基)酯磺酸钠(Aerosol-Ot,简称AOT)的浓度和水的含量不同时,溶解的CO~2对反胶束溶解牛血清蛋白(BSA)的性质和异辛烷中AOT反胶束稳定性的影响。实验表明,在适当条件下,CO~2可以使反胶束溶液中的蛋白质全部析出。本研究对有关机理进行了初步分析。     

Enhanced stabilization of reverse micelles by compressed CO2

The effect of compressed CO2 on the solubilization capacity of water in reverse micelles of sodium bis(2-ethylhexyl) sulfosuccinate (AOT) in longer chain n-alkanes was studied at different temperatures and pressures. It was found that the amount of solubilized water is increased considerably by CO2 in a suitable pressure range. The suitable CO2 pressure range in which the solubilization capacity of water could be enhanced decreased with increasing W0 (water-to-AOT molar ratio). The microenvironments in the CO2-stabilized reverse micelles were investigated by UV/Vis adsorption spectroscopy with methyl orange (MO) as probe. The mechanism by which the reverse micelles are stabilized by CO2 is discussed in detail. The main reason is likely to be that CO2 has a much smaller molecular volume than the n-alkane solvents studied in this work. Therefore, it can penetrate the interfacial film of the reverse micelles and stabilize them by increasing the rigidity of the micellar interface and thus reducing the attractive interaction between the droplets. However, if the CO2 pressure is too high, the solvent strength of the solvents is reduced markedly, and this induces phase separation in the micellar solution.     

Effect of head group polarity and spacer chain length on the aggregation properties of gemini surfactants in an aquatic environment

The aggregation behavior of cationic gemini surfactants with respect to variation in head group polarity and spacer length is studied through conductance, surface tension, viscosity, and small-angle neutron-scattering (SANS) measurements. The critical micellar concentration (cmc), average degree of micelle ionization (beta(ave)), minimum area per molecule of surfactant at the air-water interface (A(min)), surface excess concentration (gamma(max)), and Gibb's free energy of micellization (delta G(mic)) of the surfactants were determined from conductance and surface tension data. The aggregation numbers (N), dimensions of micelles (b/a), effective fractional charge per monomer (alpha), and hydration of micelles (h(E)) were determined from SANS and viscosity data, respectively. The increasing head group polarity of gemini surfactant with spacer chain length of 4 methylene units promotes micellar growth, leading to a decrease in cmc, beta(ave), and delta G(mic) and an increase in N and b/a. This is well supported by the observed increase in hydration (h(E)) of micelles with increase in aggregation number (N) and dimension (b/a) of micelle.     

Photoreactive surfactants: a facile and clean route to oxide and metal nanoparticles in reverse micelles

A new class of photoreactive surfactants (PRSs) is presented here, consisting of amphiphiles that can also act as reagents in photochemical reactions. An example PRS is cobalt 2-ethylhexanoate (Co(EH)(2)), which forms reverse micelles (RMs) in a hydrocarbon solvent, as well as mixed reversed micelles with the standard surfactant Aerosol-OT (AOT). Small-angle neutron scattering (SANS) data show that mixed AOT/PRS RMs have a spherical structure and size similar to that of pure AOT micelles. Excitation of the ligand-to-metal charge transfer (LMCT) band in the PRSs promotes electron transfer from PRS to associated metal counterions, leading to the generation of metal and metal-oxide nanoparticles inside the RMs. This work presents proof of concept for employing PRSs as precursors to obtain nearly monodisperse inorganic nanoparticles: here both Co(3)O(4) and Bi nanoparticles have been synthesized at high metal concentration (10(-2) M) by simply irradiating the RMs. These results point toward a new approach of photoreactive self-assembly, which represents a clean and straightforward route to the generation of nanomaterials.     

Formation mechanism of conducting polypyrrole nanotubes in reverse micelle systems

Polypyrrole (PPy) nanotubes were readily fabricated through chemical oxidation polymerization in sodium bis(2-ethylhexyl) sulfosuccinate (AOT) reverse (water-in-oil) emulsions. The reverse cylindrical micelle phase was characterized, and the key factors affecting the formation of PPy nanotubes were systematically inspected. AOT reverse cylindrical micelles were prepared via a cooperative interaction between an aqueous FeCl3 solution and AOT in an apolar solvent. In the H2O/FeCl3/AOT/apolar solvent system, the aqueous FeCl3 solution played a role in increasing the ionic strength and decreasing the second critical micelle concentration of AOT. As a result, AOT reverse cylindrical micelles could be spontaneously formed in an apolar solvent. In addition, iron cations were adsorbed to the anionic AOT headgroups that were capable of extracting metal cations from the aqueous core. Under these conditions, the addition of pyrrole monomer resulted in the chemical oxidation polymerization of the corresponding monomer at the surface of AOT reverse cylindrical micelles, followed by the formation of tubular PPy nanostructures. In a typical composition (74.0 wt % hexane, 22.4 wt % AOT, and 3.6 wt % aqueous FeCl3 solution at 15 degrees C), the average diameter of PPy nanotubes was approximately 94 nm and their length was more than 2 mum. The PPy nanotube dimensions were affected by synthetic variables such as the weight ratio of aqueous FeCl3 solution/AOT, type of apolar solvent, and reaction temperature. Moreover, the relationship between the diameter and the conductivity of the nanotubes was investigated.     

Effect of CO(2) and CHF(3) on the Solubilization of Protein in Reverse Micelles

The effect of dissolved CO(2) and CHF(3) on the precipitation of bovine serum albumin (BSA) from reverse micelles of sodium bis(2-ethylhexyl) sulfosuccinate (AOT) in 2,2,4-trimethylpentane (iso-octane) has been studied at 308.15 K. It was found that BSA can be precipitated completely by CO(2) while the AOT and water remain in the iso-octane continuous phase. This opens up a possibility for recovery of protein solids directly from reverse micellar solutions. CHF(3) is also an effective agent for precipitation of BSA in the reverse micelles when the expansion coefficient of CHF(3) exceeds 0.4. However, the condition required for complete removal of the BSA using CHF(3) results in some precipitation of AOT and water from the solution. Copyright 2000 Academic Press.     

Effect of Dissolved CO_2 on Protein Solubilization in Reverse Micelle

Surfactantscanformreversemicellesinapolarsolventsatsuitableconditions.Theinnerpolarcoresofthereversemicellescannotonlyhostsignificantamountofwater,butalsosolubilizepolarsolutesofdifferentsizes,suchasproteins'.Reversemicelleshavemanyapplicationsinbiotechnology.DifferentmethodshavebeenusedtocontrolproteinsolubilizationinreversemicellesinextractionandreextTactionprocesses,suchaschangingtheionicstrengthand/orPHoftheaqueousphasescontactingwiththeorganicsolventcontinuousphase',andforminggashydrates…